Diazotypes containing n-substituted p-diazoanilines having radicals of at least four conjugated c-c double bonds as n-substituents



Patented July 29, 1952 DIAZOTYPES CONTAINING N-SUB STITUTED P-DIAZOANILINES HAVING 'RADICAL'S OF ATLEAST FOUR CONJUGATED C-C DOU- BLE BONDS AS N-SUBS TITUENTS "Willard D. Peterson, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. 11 a corporation ofDelaware v NoDrawing. Application November 28, 1947, Serial No. 788,656

1 1 This invention relates to .diazotype reproducing material which will reproduce positive copies from positive originals, and more particularly to the use of diazo compounds in said diazotype materials as the light sensitive element which will decompose under exposure to long wave length light.

In the reproduction of positive copies from positive originals bythe diazotype method diazo compounds have been employed which will be decomposed most effectively. by light in the range of 3600 A. to 4200 A. The diazocompounds which have thus beenemployed hayenotbeen selected because of this'sensitivity to that range of light emanations, but have"beenselectedbecause they possess other properties which particularly suit them for use in the diazotype process; Thus these diazos will couple with azo dye coupling 4 Claims. (Cl. 957) exposure; equipment to sources-.01"; 'slight zuzliieh components in the proper coupling medium or atmosphere to produce .d-yeimages in a wide range 'of colors, particularly in deep shades. They also can be incorporated together with the coupling component in a two-component diazotype system and stored forreasonable lengths of time without danger of coupling taking place prior to exposure and development. They will also, under proper conditions, produce washfast images which will not bleed to any appreciable extent. Those diazo compounds which have been found to possess these properties requisite for efficient diazotype reproduction embrace for the most part monodiazo derivatives of p-phenylene-diamines wherein the undiazotized amino group may besubstituted by simple substituents such as alkyl, alkylol, phenyl. and substituted phenyl and'the like. Diazo derivatives of o-amino naphthols have also been employed to some extent and monodiazo derivatives of ophenyldiamines where the undiazotized amino group is at least mono-substitutedby one of the above-mentioned substituent groups have been suggested, but are of little importance commercially. These diazo compounds which have been found mostsuitable for diazotype reproduction work as indicated above are most effectively decomposed by sources of light emitting rays in the 3600A. to 4200 A. line. In general, it can be said that diazotype materials hereto fore employed are decomposed only by Wave length of light shorter than 4800-5000 A.

In order to meet the light requirements of .these diazotype materials and of other "photoprinting. materials suchas'blueprints, and silverisalt'sensitized' photo materials such ':as 'so-calledfvan Dyke -paper, it has been' necessary to confine are rich. .in :emanationsroi rays. having .wave lengths in the 3600-4200 A. range Whenusi-ng incandescent Llamps .a's th'e light source in order to produce a Hsufiicient con'ceritrationof such rays, it-.'is nec'essaryitooperate the inoandesce'nt lamps at-higher voltage than lbulb lifeconsi-d'erations permit. Since incandescent lamp's :emit light which is particularly'rich in wave lengths above thei4000 line they constitute a -wasteiul source of energy for this purpose. Untilethe advent of -the high pressure -mercury --quai 'tz-arc lamp which eflici'ently'emits light -rich' in wave lengths within menace-4200 42; range; 'expo sure devices for diazotypes'and pther photoprinting materialshavin'g-the' same "light sensitive foh are acateristics made use of carbonarclamps and low pressure mercurywapor tubes which have definite operational disadvantages; The high- It hasnow beendiscovered' that-1 a new class of diazo compoundsnot-"heretofore employedifor' diazotype :or photosensitive printing-may "-beat. fectively employed "in diazotypes and: effi'-' cient-ly decomposed*byi'light havinglonger wave:

lengths -such as5200-"6000 These'i-are waive len ths f li ht wh h a e rnmm ll temit by fl o s amp in ande c n f'p ib oifiood and other types of incandescent lamps. Consequently, when' usingsuch diazo -c'ompounds as the light sensitive'elementpf the photo reproduction material the exposure may be carried out by using equipment containing fluorescent lights which may be a simple portable lamp or a portable unit containing incandescent photoflood lamps, thus makingxpossibleyefficientexposure of a. photoprintingmaterial bya small user who is limited to portable,-easily operated units. The new c1ass..of,diazo compounds will also decompose efliciently upon exposure to presently used sources of light which operate most efficiently in the shorter wave length ranges,

such as the 3600-4200 A. range, to which present diazotype materials are most sensitive.

The new class of diazo compounds may be defined as'N-substituted p-diazoanilines inwhich the substituent 'or ssubstituents on the. amino group contain at least four conjugated carbon to carbon bonds in a cyclic nucleus. The diazo compounds of this class are diazo derivatives of amines which may be represented by the for- '5'-(4-amlno-2-carboxyphenylamino)-quinollne-4-carboxyllc mulae:

- R1 and wherein R1 contains at least four conjugated carbon to carbondouble bonds innan aromatic orheterocyclic ring system; R2 is a heterocyclic trifiuoride, zinc chloride, cadmium chloride,

naphthalene disulfonic acid, and the like.

Diazo compounds of this class can be readily prepared by the diazotization of the corresponding amine and the formation of the diazo complex by the usual methods. The amines .may be prepared by one of the following methods.

(1) reaction of p-phenylenediamines with hydroxy aromatic compounds containing four conjugated double bonds at elevated temperatures in the presence or absence of. sodium bisulfite, [Bucherer, J. prakt. Chem. (2) '70, 345 (1904)]. (2) reaction of a primary amino group of a compound containing four conjugated double bonds with a 1-halogen-4-nitro-benzene which may posess a carboxy or sulfo group in the 2- position, and reduction of the nitro group to the corresponding amino, EGoldberg, Ber. 40, 4543, 4545 (1907) and German Patent 164,504].

(3) reaction of a halogenated compound containing four conjugated double bonds with a monoacylated p-phenylene-diamine, followed by hydrolysis of the acylated amine.

(4) reaction of a heterocyclic compound containing four conjugated double bonds and a -NH group as a part of the heterocyclic ring, with a nitrobenzene in the presence of alkali, [Helv. Chim. Acta 6, 94-101 (1923) 1.

Examples of amines of this class prepared by one of the above reactions are as follows:

N- (4-aminophenyl) -1 -anthramine V ONE? 5 (aminophenylamlno) -1, S-naphthosultan 6- (aminophenylamino -2-methyl-4-phenylquinoline HOOC NH I NH;

COOH

2- (2-methyl-4-quinolylamino -5-aminobenzenesulfonic acid NH NH:

3-(4-aminophenylamino) -9-ethylcarbazole @O-NH-O-NH, I

' 5-(aminophenylamlno)-1-ethylindo1e 1 (4-aminophenylamino) -5-benzamldoindole moo In the preparation of the diazotype material in accordance with this invention the diazo compound is applied to a suitable carrier such as paper, a regenerated cellulose. cellulose ester or cellu ose ethe s ip. a glass plate. textile. ma.- e ial, a sela ed'su ac crmetallicysu iace, b i t ns sprayin th said; arrier with "a p eparen n a i ea edi zo compoundhan c c p s co onent su as a phenolic sub,-

, ing light. having long wave lengthsin therange of 520043.000 A. such as aiiucrescent light .or a incandescent. photofiood lamp. It is then devel- Oped by contactingthe exposed sensitized surface with ammonia vapor or other suitable alkaline materials. As the diluent tforthe coating *solution-organic solvents of .high ,volatility-suchas alicohols, particularly isopropyl alcohol,.ethers-and.

ketones, as for example, acetone, may be employed either wholly or partially in place of the water, particularly when the film materials of re-.-

generated cellulosercellulose esters, or cellulose ethers are employed asthe" carrier.

In another manner of carrying out theprocess the diazo compound may be added to the coating solution as the only azo dye component and the solution coated onto the carrier in the same manner. The exposure under a suitable positive or negative picture, drawing or the like is effected as before but the image is developed by bathingthe exposed element in an alkaline bath containing the azo dye coupler necessary to couple with the undecomposed diazo to form the. desired azo .dye in the unexposed areas.

As coupling components for the production of A e he selected suppor orbase, hasa..-e1.ea.t er; ce taae of: the total radiationgof hi hsress. uartzamercury ar lamnsrthanithc diazo. m terials which are sensitive only to the. horter wav len ths. flfhisnwid r utility of t e totalmadiation ircm such a light source. is-:also= due to :the. -.fac that; themew di om nd u ilize one 0,1 the major, emission :bands in the:

' green region oft-the spectrum which is 5&100-16000 trast than conventional diazotype materialswhen thedyeimage by developing'the residual unde composeddiazo compound in the density areas,

any compound which will function as a coupling component may be employed either in the coating composition or with the-diazo compound as a two-component system or in thedeveloping solution as a color forming -develperto. be used with a single component -diazotype system. In eitherrcase, thecoupling component selected will be one which willproduce the desired color or a combination of coupling componentswhich will produce a desired multi-color 'eiifect. Examples of preferredcoupling, components are-the sodium salt of 2-amino-8-naphthol-3,fi-disulfonic acid,

2,3-dihydroxynaphthalene or; its 6-,- sulfonic acid or sodium sulfonate derivative. c naphthol-iifidisulfonic acid, ..2,7 -dihydroxynaphthalene, 1,7- aminonaphthol, 2 hydroxynaphthalene 8 biguanide, 1-amino-8enaphthol-llfi disulionic acid, l -naphtholi sulfonicacid, l-naphthol-3,8-disulfonic acid, phloroglucinol and resorcinol der iv, atives such as resorcinol monoacetate, m-hyacetoacetanilide,v -'7.-'-hydroxydroxyphenylurea, LZ-naphthamidizole, '7-hydroxynaphthalene-lbiguanide and cyclohexyl acetoacetamide.

Although the diazo-compounds of this invention are particularly sensitive-to long wave light of wave lengths greater than 4200' A. and as high as 6000l n, whichwave lengths are emitted by fluorescent lights, they are also sensitiveto'shorter wave length light, l and in 'view" of- "this dual sensitivity as compared with "diazo compounds "here-'- tofore employed in diazotype production, which latter do not enjoy the long wavesensitivitythe new diazo compounds permit "the utilization pt A The. net,v effect: of;- this: property of Y the new diazo: compounds: isan increasedspeed; of decomposition. or: increased, printing, speed, as -com pared. withdiazo com-pounds heretofore -em-- played when using the-high pressure mercury arc lamp :as .the light source for exposure, which lightsource isextensively inuse. Thenewdiazo compounds therefore have a two-fold advantage over .di'azo. compounds-heretofore employed, one

being the: increased printing speed when using,

conventional sources of light and the second being the adaptability to sources of light which are poor in shortwave-emanations, that is, less than 4200 A, but .richin long-wave emanations;

above that band. The. new diazo compounds also have the. ad

vantage due to their sensitivity'to longer wave length ,light of. producingprints of greater-conused in the intermediate or transition diazotype printing process. In. the preparation of intermediate or transitiondiazotype copies where a diazotype transparency is first {produced on transparentized paper or cellulosic film which has been sensitized to produceadye image highly absorptive of ultraviolet light, a diazo compound which is sensitive to light of a wave length of from-36.004200, or 4500.- A. is transformed by the usual diazotype methods'to'an azo dye-print havinga-maximum absorption in the range of 4000- 5000' A. In the printing of further-copiesfrom such an intermediate or transition copy better prints are obtained" if'a diazotype paper can be used which is sensitive to lightin'the range of 4000-5000 A; than will be obtained by using a paper-sensitivetothe range of 3600-45001. The

intermediate prints, therefore which are made. with conventional diazotype. materials, do not e'fiiciently yield diazotype copies with present diazotype materials since the azo dye images of the intermediate print do not eificiently absorb light having the shorterwave lengths and consequently, a portion or the diazo under the dye image is affected. Iidiazotype papers containing the new diazo compounds of this mention are employed, more satisfactory prints will be obtained in'view of thesensitivity of the new diazo compounds to the longer wave length light.

In the following specific examples the preparation of a number ofrepresentative diazo com-- pounds of the above class is set forth and the results obtained by using these diazo compounds in typical diazotype coatings are indicated. It is to be understoodthat these examples are presented as illustrations of the preferred manner of carrying out the invention but not as limitationsof its scope- Unless otherwise stated, parts givenarefby weight. 1 I

Example-1.+4 diczophenyl-anaphthylamine A mixture of 13.5 parts of 4-aminophenyla naphthylamine [prepared by the method of .J.

prakt. Chem.(2-) ,60, 557 (1899) l, 125 parts Water and 18 parts concentrated hydrochloric acid is hours and filtered. To the filtrate is -added 17 parts of an 85% solution of zinc chloride' The brown solid whichseparates is recovered by filtration. Diazotype coatings of. the. materialin conjunction with resorcinol, 1-phenyl1-3-methylpyrazolqne and 2,3-dihydroxynaphthalene gave brown, orange andpurple prints respectively. 1

A' mixture of 1.0'part of the zinc chloride complex of 4-(a-naphthylamino) -benzenediazonium chloride, 1.5 parts citric acid, 1.5 parts thiourea, 50 parts water and 0.25 part ofv 3,5-dihydroxybenzoic acid is coated on rag sulfite paper, This coating shows sensitivity tolight, having wave lengths betwen 3250A. and 5200 A. with a maximum sensitivityof 4350 A. Thesevalues may be compared with the sensitivity .of p"-diethylaminobenzenediazonium chloride complex of zinc chloride, which is sensitive to light in the range of 3500-4600 A, with a mammum sensitivityat 4100 A. I I

7 Example 2.-4-dia20phenyl-smaphthylamifie nus-4126 I A;'mixture of 12 partsof p-aminophenyl-pnaphthylamine [prepared bytheprocess of J. prakt. Chem. (2) 75, 249-831 is added to a boiling mixture of 190 parts water and 6 parts concentratedhydrochloric acid. 1 To this mixture,v is

added'l2 parts ofv concentrated hydrochloric acid.

The mixture is cooled to .3 G and 40 parts of molar sodium nitrite solutionfis added;; ;This' mixture isstirred for 18 hours and the excess nl: trite is destroyed by the addition of urea and the mixture is filtered. To the filtrate is added parts of-concentrated hydrochloric acidiand l8. partsof an 85% solution ofzinc chloride. fIhe mixture is cooled and filtered. A yellow-orange.

solid, which is'recovered; is coated on paper.-

Coatings of the diazonium complex -with resorcinol, il-phenyl-3-methylpyrazolone and. 2,3

dihydr'oxynaphthalene gave brown, orange-red and purple prints respectively.

It was found that the .4-(B-naphthylaminob benzene-diazonium complex of zinc ,chlorideis light sensitive in therangeof 3600-5400 A. with a maximumsensitivity at {1700 A. r

Example 3..-2 rp d a e ene-a suzj mc acid; a

naphthalene-G-sulfonic acid, 120 parts water, 30

parts p-phenylenediamine dihydrochloride and 500 parts sodium bisulfite is'heated under reflux for 16 hours; then one steam bath for an additional 24 hours. '-The solution is cooled and liltered. Upon drying, a'fine powdery solid is obtained.

A mixture of 6.7 parts of 2-(p-aminophenylamino)-naphthalene-6-sulionic acid, 0.8 part of 8. sodium hydroxide and 90 parts ofwater are heatedto boiling-to' dissolve the solids. The mixture is cooled and l part of concentrated hydrochloric acid is added. To the stirred mixture is added asolutionof 2.1 parts sodium nitrite-in 5 parts of water; The solution was heated and added dropwise to a mixture of 17 parts of concentrated hy-- drochloric acid and 2.8 parts of an solution of zinc chloride. This mixture is stirred for 24 hours, cooled and filtered. A black sticky product, upon drying, is converted to a black powdery solid. Diazotype coatings of the dia'zo complex with resorcinol, phloroglucinol and 2,3-dihydroxy-naphthalene gave brown, brown and purpleprints-respectively. Q

A coated paper using diazotiz'ed aminq phenyl-B-naphthylamine as the light-sensitive 3 /2 minutes exposure to the fluorescent lampto' give a comparable print, i. e., the printing speed of the new material is nearly double that of the fastest diazotype material now produced when printed by means of a fluorescent light, as a source of long wave length light.

Example 4.N-(p-diazophenyl)-carbazole v To a hot solution of 29.4 parts of N-(p-aminophenyl) -carbazole [prepared by the'method of Helv. chim. Acta 6, 94101 (1923)] in 300 parts of formic acid was added 10.1 parts of concentrated hydrochloric acid. On cooling the solution to 10-15 0., a white precipitate was noted. To the suspension at 10 C. was added dropwise, over a period of 45 minutes, 21 parts '7. of 5 molar sodium nitrite solution. A trace of sulfamic 'acid'was added to destroy the excess ni trite. To the mixture was added 320 parts of a 10% solution of naphthalene-1,5-disulfonic acid.

A yellowish-brown crystalline solid, amounting to .33 parts, was isolated by filtration. The solid was found to be 93% pure on the basis of a diazo nitrogen analysis. Diazotype coatings of the com-' plex' with resorcinol yielded an orange-brown print.

parts of citric acid and 50 parts of water was coated on rag sulfite paper.

of 4000-5900 A y with a maximum sensitivity of 4950 A.

Example 5 .2- p-amz'nophenylamz'no) -quino lznc;-

- A mixture of 200 parts of 2-chloroquin6line and parts of p-aminoacetanilide is heated gently.

The mixture melts at 91100 C.; then an exother- A solution of 1.8 parts of Q-(p-aminQphenyD carbazole diazoniumzinc chloride complex, 5

This material was found to be sensitive to light having a wave length ethanol, parts of concentrated hydrochloric acid was heated for a few minutes, then filtered to remove insoluble material. The filtrate was refluxed for 2 hours. A crystalline yellow solid separated and was recovered by filtration, then washed with ethanol and ether. This material was shown by analysis to be the dihydrochloride of 2-(p-aminophenylamino) -quinoline.

A mixture of 11.7 parts of 2-(p-aminophenylamino) -quino1ine, 50 parts of water and 20 parts of concentrated hydrochloric acid is cooled to 0 C. A solution of 3.5 parts of sodium nitrite and 7 parts of water is added dropwise over a period of minutes and the mixture stirred for an additional 30 minutes. A yellow precipitate, which formed, is dissolved by adding 500 parts of absolute alcohol to the mixture. The mixture is cooled to l0 C. and filtered. The product. amounting to 13 parts, is purified by dissolving 6 parts of the material in 350 parts of water, cooling to 0 C. and adding 40 parts of 85% zinc chloride. The brilliant yellow solid, which formed, is cooled and dried in vacuo.

Coatings of this material with sodium 2-hydroxy naphthalene 3,6 disulfonate, 2,3 dihydroxynaphthalene and phloroglucinol gave red, brown and yellow diazotype prints respectively.

I claim:

1. A diazotype material comprising an insoluble support having a non-colloidal coating containing a light sensitive diazo derivative of a p-phenylenediamine of the following formulae:

wherein R is a member of the group consisting of hydrogen, alkyl, and substituted alkyl; Y is a member of the group consisting of hydrogen, carboxyl and sulfonic acid radicals; R1 is a member of the group consisting of aromatic and heterocyclic radicals of the naphthalene, anthracene,

quinoline, carbazole, and indole series; and R2 is a heterocyclic ring system containing the N atom as a hetero atom selected from the group consisting of indole and carbazole ring systems.

2. A diazotype material comprising an insoluble support having a non-colloidal coating containing as the light sensitive agent a diazo derivative of 4-aminophenyl-u-naphthylamine having the structural formula:

and an azo dye coupling component.

4. A diazotype material comprising an insoluble support having a non-colloidal coating containing as the light sensitive agent a diazo derivative of N-(p-aminophenyl) -carbazole having the structural formula:

and an azo dye coupling component.

WILLARD D. PETERSON.

NaOsS REFERENCES CITED The following references are or record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,756,400 Schmidt et a1 Apr. 29, 1930 1,758,676 Schmidt et al May 13, 1930 1,983,005 Sakurai Dec. 4, 1934 2,100,063 Zahn Nov. 23, 1937 2,277,409 Murray Mar. 24,1942 

1. A DIAZOTYPE MATERIAL COMPRISING AN INSOLUBLE SUPPORT HAVING A NON-COLLOIDAL COATING CONTAINING A LIGHT SENSITIVE DIAZO DERIVATIVE OF A P-PHENYLENEDIAMINE OF THE FOLLOWING FORMULAE: 